Production of compounds of esters of strong acids with anthrapyrimidines



Patented Sept. 29, 1936 UNITED STATES PATENT OFFlCE PRODUCTION OF COMPOUNDS F ESTERS OF STRONG RIMIDINES ACIDS "WITH ANTHRAPY- No Drawing. Application March 9, 1935, Serial No. 10,332. In Germany March 14, 1934 14 Claims.

The present invention relates to compounds of esters of strong acids with compounds of the anthrapyrimidine series and a process of producing same.

I have found that compounds of esters of strong acids with compounds of the anthrapyrimidine series are obtained by heating compounds of the anthrapyrimidine series with esters of strong acids substantially in the absence of water.

The reaction is preferably carried out in the presence of an inert organic diluent, as for ex ample nitrobenzene, trichlorbenzene, dichlorbenzene, benzene or toluene. The anthrapyrimidines may also be brought directly intoreaction with the said esters.

Compounds of the anthrapyrimidine series suitable for the purpose of my present invention are for example anthrapyrimidines, anthrapyrimidones, anthradipyrimidines, anthrapyrimidinopyrimidones and derivatives of these compounds, as for example their halogen, hydroxy, mercapto, nitro, amino, alkyl, such as methyl or ethyl methoxy and arylido compounds.

Esters of the said kind are for example the esters of halogen hydracids, as for example methyl chloride, methyl iodide, ethyl bromide, or of sulphuric acid, as for example dimethylsulphate or diethyl sulphate, or of phosphoric acid, or of arylsulphonic acids, as for example esters of the orthoand paratoluenesulphonic acids.

The reaction is generally speaking carried out at elevated temperatures. The yields are usually very good and in many cases even amount to those theoretically calculated.

The compounds obtainable according to the present invention usually dissolve comparatively readily in water and solvents which behave similarly to water. They may be employed as such or as intermediate products for dyestufi chemistry, pharmaceutical chemistry and in the photographic industry. I

The following examples will further illustrate how my said invention may be carried out but the invention is not restricted to these examples. The parts are by weight.

Example 1 A mixture of 100 parts of pure 4-amino-1.9 anthrapyrimidine (prepared by the sublimation of crude 4-amino-1.Q-anthrapyrimidine or by the purification of the said compound by way of its sulphate), 90 parts of para-toluenesulphonic acid methyl ester and 1000 parts of trichlorbenzene is boiled for an hour. After cooling to about 100 (3., the yellow-red crystals obtained in a yield of from 95 to 100 per cent of 4-amino-L9-anthrapyrimidine with para-toluene-sulphonic acid methyl ester which probably has the following formula:

ll 0 NHz are filtered off by suction. They dissolve in concentrated sulphuric acid giving a red coloration and in thin layers giving a blue-red coloration; the coloration becomes deep-blue-red by the addi tion of formaldehyde. The compound is also readily soluble in Water giving a yellow-red coloration. It may be crystallized from water. It dissolves only with great diificulty in organic solvents free from hydroxyl groups, as for example trichlorbenzene or nitrobenzene, but more readily in alcohols, ketones or phenols.

The aqueous solution of the compound becomes blue-red upon the addition of the caustic soda solution; the alkaline hydrosulphite solution is brown; the latter dyes vegetable fibres reddish yellow shades.

The following table gives the properties of some compounds of anthrapyrimidine and its derivatives with esters of the kind defined above.

Initial material Ester Resulting compound 1.9 anthrapyrimi- Para-toluene- Brown needles. Dissolve in dine sulphonic sulphuric acid giving a acid methyl green-yellow coloration and ester readily soluble in water giving a yellow color 5 amino 1.9 -an- Para-toluene- Violet needles. Dissolve in thrapyrimidine sulphonic sulphuric acid giving a acid methyl green-yellow coloration and ester in water giving a violet coloration 8 amino 1.9 an- Para-toluene- Blue crystals. Dissolve in thrapyrimidine sulphonic sulphuric acid giving a acid methyl green-yellow coloration; ester readily soluble in water giving a blue coloration 2 amino 1.9 an- Para-toluene Orange crystals. Give a .thrapyrimidine sulphonic violet coloration in sulacid methyl phuric acid; readily soluble ester in water giving an orange coloration 4 -para chlor -ben- Para -toluene- Yellow crystals. Give redzoyl amino 1.9 sulphonic dish yellow coloration in anthrapyrimidine acid methyl sulphuric acid and greenester yellow in water Initial material Ester Resulting compound 5 para toluldine Para-toluene- Violet crystals. Give yellow LQ-anthrapyrimisulphonic coloration in sulphuric acid dine acid methyl and blamed in water ester iamino-C-phenyl- Para-toluene- Orange crystals. Give or- 1.9 -anthrapyrim1- sul phonic ange red coloration in suldine acid methyl phuric acid (in thin layers, ester violet) and orange in hot water 4-amino-L9-antl1ra- Para-toluene- Orange crystals. Give yelacid; readily soluble in water with orange color Orange-red crystals. Orangered in sulphuric acid; readily soluble in water with yellow-orange color i-amino-LQ-anthra- Ethyl bropyrlmidine mide 4-amino;1.9-anthra- Dimothylsul- Yellow-orange crystals. Yelpyrimidine phate low-red in sulphuric acid; very readily soluble in water with yellow-red coloration 4-l1ydroxy-L9-an- Para-toluene- Yellow crystals. Yellow-red thrapyrimidine su lp h o n i c in sulphuric acid; readily acid methyl soluble in water with yelester low coloration 4 -methylamino-l.9- Para-toluene- Orange crystals. Orange-red anthrapyrimidme so 1 ph cnic in sulphuric acid; orange in acid methyl water ester Py-C-aminq-l il-an- Para -toluene- Yellow-orange crystals. Readthrapyrimidme sulp honic ily soluble in water with acid methyl yellow-orange color es er 4-aminol.9-anthra- Diethyl sul- Yellow-orange crystals. Yelpyrimidine phate low red in sulphuric acid; very readily soluble in water with yellowred coloration 4-hydroi'iy1 dichlor- Para -toluene- Yellow crystals. Yellow-red 1.-ant rapyrimi- 5 111 p honic in sulphuric acid; readily dine acid methyl soluble in water with ester yellow coloration Beta-methyl 5+ Paratoluene- Orange crystals. Y ell ow amino -l.9-anthrasu lphonic orange in sulphuric acid; pyrimidine acid methyl readily soluble in water ester with orange coloration Py- 0 -methyl 4 Para -toluene- Yellow-orange crystals amino-1.9-anthrasulphonic Readily soluble in water pyrimidine acid methyl with violet coloration ester 1.9.4.10 anthradi- Para -toluene- Yellow crystals. Readi ly pyrimidine s u l p honic soluble in water with actid methyl yellow coloration es er Amino- 1.9- anthra- Para -toluene- Blue crystals. Y ellow in pyrimidine (from sulphonic sulphuric acid; readily anthrapyrimidine acid methyl soluble in water with by nitration and ester violet coloration reduction).

In addition to the said compounds of the anthrapyrimidine series, many other compounds of the said series may be employed as initial ma.- terials, such as chloror Dram-1.9 anthrapyrimidines, amino-halogenor acetylamino-LS- anthrapyrimidines, urea derivatives of 1.9-anthrapyrimidine, arylidoand dialkylamino-1.9- anthrapyrimidines and diazo salts of amino-1.9- anthrapyrimidines. Instead of the esters stated,

r other esters may be employed as for example orthotoluene-sulphonic acid esters, benzene-, tolueneor naphthalene sulphonic acid phenyl esters, octodecyl bromide, ootodecyl chloride, vinyl chloride, butyl bromide or diethyl sulphate.

Instead of trichlorbenzene, dichlorbenzene, mono-chlorbenzene, nitrobenzene, pyridine, benzyl ether or diphenyl may be employed as diluents.

Example 2 A mixture of 50 parts of 4-hydroxy-L9-anthrapyrimidine, 500 parts of trichlorbenzene and 75 parts of dimethyl sulphate is heated at between 155 and 160 C. for 15 minutes. After cooling the crystalline reaction product is filtered oil by suction. It is obtained in a yield of 7 5 parts. It dyes animal and vegetable fibres very fast brown shades.

Example 3 A mixture of 137 parts of 2-brom-4-benzoylamino-1.9-anthrapyrimidine and 300 parts of methyl iodide is heated, while stirring, in an autoclave at 150 C. for 6 hours. After cooling the excess methyl iodide is removed by distillation or by filtering oil the reaction product. The new compound forms yellow crystals which dissolve in Water giving a yellow coloration which turns violet-red upon the addition of sodium hydroxide solution. It dyes vegetable and animal fibres greenish yellow shades.

Example 4 A mixture of parts of 4-amino1.9-anthrapyrimidine and 500 parts of the normal ester of phosphoric acid with chlorethyl alcohol is heated while stirring at C. for a short time. As soon as a. sample withdrawn has become readily soluble in water, the reaction mixture is allowed to cool. The reaction product is then filtered 01? by suction. It forms brown-red needles which dissolve in water giving a red coloration which upon addition of sodium hydroxide solution turns olive-yellow. The compound dyes vegetable and animal fibre orange shades.

What I claim is:

1. Compounds of esters of strong acids with anthrapyrimidines.

2. Compounds of esters of strong acids with 1.9-anthrapyrimidines.

3. Compounds of esters of strong acids with amino-1.9-anthrapyrimidines.

4. Compounds of esters of strong acids with hydroxy-LQ-anthrapyrimidines.

5. Compounds of esters of strong acids with halogen-LQ-anthrapyrimidines.

6. Compounds of esters of strong acids with it-amino-1.9-anthrapyrimidine.

7. Compounds of esters of sulphuric acid with anthrapyrimidines.

8. Compounds of esters of halogen hydrides with anthrapyrimidines.

9. The compound of toluene sulphonic acid methyl ester with 4-amino-L9-anthrapyrimidine.

10. The compound of dimethyl sulphate with e-hydroxy-1.9-anthrapyrimidine.

11. The compound of methyl iodide with 2- brom-4-benzoylamino-LQ-anthrapyrimidine.

12. A process for producing compounds of esters of strong acids with anthrapyrimidines which comprises heating anthrapyrimidines with esters of strong acids substantially in the absence of water.

13. A process for producing compounds of esters of strong acids with anthrapyrimidines which comprises heating anthrapyrimidines with esters of strong acids in the presence of an inert organic diluent substantially in the absence of water.

14. A process for producing compounds of esters of strong acids with anthrapyrimidines which comprises heating anthrapyrimidines with esters of strong acids in the presence of a halogenated hydrocarbon.

KARL KOEBERLE. 

